Mineral oil composition



Fatented Dec. 7, 1948 1 UNITED STATES PATENT OFFICE a l} a ..;i12",45 5,66s T i y I h H h i h fkivnnnahn OIL COMPOSITION and Henry S; AngeLWoodbury,

N. J., assignors to Socony-Vacuum Oil Com- .pany, Incorporated, a corporationof New York No Drawing. Application May 3, 1945,

a se -arm. 591,840

I This invention hasto do of viscous mineral oil fractions against the delee terious efiects of oxidation or deterioration with use bythe addition thereto of oxidation inhibitors. directed to theimprovement of viscous mineral oil fractions by the use of a combinationof such inhibitors, namely, a primary oxidation inhibitor and a secondary inhibitor, which when admixed with a viscous mineral oil in minor proportions will preventfor delayundesirable changes taking place in the oil. y I

As is well known tothose familiar with the art, substantially all of the numerous fractions obtained frommineral oilsand refined fortheir numerous uses are susceptible to oxidationlbThe susceptibility of an oil fraction to oxidation and the manner in which oxidation manifests'itself within the oil varies with the type and d'egreegof refinement to whichithe oilhas been subjected and with the conditions underfwhich it is used or tested. That is, the products formed in anoil fraction asa"result' ofpxidatior'i and the degree with the; amma;

More specifically, the "present invention is to which they are formed depends upon the extent to which the various unstable constituents or constituents which mayact as oxidation catalysts have been removed byrefining operations, and also upon the conditions of use. ,1

x The present invention ispredicated upon the discovery that the oxidation characteristics of viscous mineral oil fractions are greatly improved by the incorporation therein of. minor proportions of each of two inhibitors which are designated herein. as primary oxidation inhibitors and secondary inhibitors. C i y. :y; I

The primary oxidation inhibitors contemplated herein are phosphorusand sulfur-containing reaction products obtained by reaction, at a temperature above aboutJOO" CL, .of a phosphorus sulfide and a dicyclic terpene or a materialpredominantly comprised of a dicyclic; ,terpenet v All of the phosphorus sulfides, such asiPaSs ,(or PS2), P4Sc (0r .PzSa), P4Ss, P285, P4S'r, P4810; etc. arecontemplated as reactantsin thepreparae tiontof l primary oxidation inhibitors; however; P255 is particularly preferred; As usedwherein the designation dicyclic terpene refers to those terpenes which are characterized by the presence of one double bond in the molecule and arebtiilt up of two ring systems. Illustrative of such compounds are pinene, camphene and fenchene. Also contemplated as coming within this particular designat'ion are those materials which are predominantly comprised of one or moredicyclic terpenes; representative of. such materials are the essential or volatile oils which are predominantly comprised ofsuch a terpene or terpenes and are typified by turpentine oil, the predominant constituent of which is pinene. Particular preference is accorded to pinene and turpentine oil. 1 i

It is also to be understood that the aforesaid designation dicyclic terpene is not inclusive of such terpenes as those known in the art as monocyclic terpenes, which are typified by dipen'tene and terpinolene. Finally the dicyclic terpenes are not to be confused with the olefin hydrocarbon terpenes such as myrcene.

Although a complete understanding of the chemical composition of the reaction products of phosphorus sulfides jand dicyclic lterpenesj is not realized at this time, a partial understanding of their composition may be realized by noting the characteristics involved in the reaction. ForeX- ample, the reaction of phosphorus pentasulfide and pinene commences at about C. andis exothermicin nature. During the reaction, the reactionlmix ture increasesiappreciably in viscosity andlittle ifhanylhydrogen sulfide is evolved therefrom. The reaction,productobtainedln this reaction contains phosphorus and sulfur in sub stantially the same amounts as in the phosphorus sulfide used. It would appear then that the reaction is one of addition, thatis, addition of phosphorus sulfide to the one unsaturatedbond prese v ing ie ea .v v t :1 t

While the reaction temperature for the reaction described above should be. one of at leastuabout 100? C., the preferred temperatures ifall within lthe range of about 100 C. toabout .C. y i

The proportions of reagents used in the preparation of theprimary oxidation inhibitors may be varied in order toprepare reaction products having difierent degrees of-oil solubility and different degrees of oilimprovingpowern In this regard, it is preferred that about one mol of phosphorussulfidegbe reacted with four. mols of a dicyclic terpene in order to obtain a reactiontproduct relatively soluble in petroleum 0115; (For. example, whenmorethone 101161110101: PzSs is used with fourtmolsof 'pinene, a viscous gel-like -re' action is obtained and this product'is definitely insoluble in. petroleum oilsl Also when lessthan one molof Pass isjused with four mols ofpinene a :viscous as somewhat insoluble in mineral oils is obtained; after "the unreacted pinene has been removed by distillation-F Accordingly, it is l to be understood that while eifiectiveprimary oxidation inhibitors can be obtained by using different ratios of reactants;particularly preferred inhibitors are those obtained by using approximately one mol of a phosphorus sulfide for about four mols of a dicyclic terpene.

ihere is, however, still another desirable procedure for preparing the primary oxidation inhibitors. In order to obtain a relatively nonviscous reaction product, a blend of dicyclic terpene, such as pinene, and a comparatively inert solvent, such as petroleum oil, may be treated as, described above to provide an oil blend of the reaction product. The preferred procedure of this type involves the use of a 1:1 blend of dicyclic terpene and petroleum oil with a phosphorussulfide; the molar ratio of said terpeneto said-sulfide being about 4:1.

The aforesaid primary oxidation inhibitors effeet improvement of several of the oxidation-characteristics of viscous mineral oil fractions when used therein in small amounts, improvement during use being effected, for example, by the prevention of corrosion of hard metal bearings, the inhibition of acidformation, the inhibition of forma'ti'ojnof gummy deposits in engines, the inhibition of increase in viscosity, etc. Such oil fracti'ons containing only primary oxidation inhibitors, however, are undesirable from the standpoint of solubility stability, or resistance to haze formation'. On standing for several days or when heated and then left to stand, an oil composition comprised of a", viscous mineral. oil fraction and a primary oxidation inhibitor tends to become cloudy. This shortcoming has now been overcome by incorporating a small amount of a sec oridary inhibitor in such an oil composition.

' The secondaryinhibitors'of this invention which are capable of regulating or preventing the aforesaid haze problem are esters of organic carboxylic acids and wax-substituted.hydroxyaromatic compounds. While the foregoing langauge is an accurate definition of the esters contemplated herein, they may also be designated as esters obtained by reacting an acid chloride (corresponding to the organic carboxylic acid) with a waxsubstituted hydroxyaromatic compound; this is the preferred method for preparing the esters. Typical esters of this class are those obtained by reaction of benzoyl chloride and wax-substituted phenols, the esters being identified as wax-substituted phenyl benzoates. Preferred, for the purposes of this invention, in view of'their' outstandingcooperative action with the aforesaid primary oxidation inhibitors, are wax-substituted phenyl benzoates and phthalates, particularly preferred of which are the tetrawax substituted benzoates and phthal'ates. Inasmuch as those esters are well 'known in the artand are described at length in Patents Nos. 2,048,465, 2,048,466 and 2,138,809, issued to Orland M. Reid and Darwin E. Badertwhen it' is believed to beunnec'essary to do other than brieflyillustrate the same hereinafter.

The particularly preferred compositions of primary and" secondary inhibitors in viscous mineral oil: fractions which are contemplated herein are those in which. the: primary inhibitor is a P2S5- pinene reactionproduct or aPzss-turpentine oil reaction product, and the secondary inhibitor is either" tetrawax-substituted phenyl benzoate or tetrawax-substituted phenyl phthalate.

To illustrate the primary oxidation inhibitors contemplatedherein several typical inhibitors of this class were prepared as described in Examples I thrpughIV whichfollow.

Two hundred grams, (1.4!? mol) of pineneand 4 41 grams (0.185 mol) of P285 were warmed up gether with stirring for 1 hour with rising temperature, the maximum temperature being 160 C. There was practically no evolution of hydrogen sulfide during the reaction and the reaction mixture was a dark-orange, viscous oil. On distillation at 5 mms. pressure and maximum; temperature of 150C" '70'grams" (0.51mol) of pinene were recovered. The residual oil was analyzed and found to contain 16.7 per cent sulfur and 6.0 per cent phosphorus. This product will be referred to hereinafter as Product I.

EXAMPLE II A blend of grams of pinene and 100 grams of a motor oil (Saybolt Universal viscosity (S; U. V.) of 45 seconds at 210 F.) was heated with 41 grams of P285, the molar ratio of pinene to PzSs being 4:1. An exothermic reaction took place with the temperature rising to a maximum of: 190 C. for a few minutes. The reaction mixture was filtered after it had been cooled and after several grams of clay were added thereto. The filtrate was a viscous oil containing 11.7 per cent sulfur and 4.78 per cent phosphorus. This product is-identified hereinafter as Product II.

EXAMPLE III Eight hundred grams of pinene and 800 grams of a motor oil (SayboltUniversalviscosity (S.U.V.) of 45 seconds at 210 F.) were heated to C. with stirring. 326.4 grams of P255 (a ratio of 4 mols of pinene to 1 mol of P285) were added slowly, the temperature rising to C. because of the exothermic reaction. The mixture was then heated to C. for 1 hour, 32 grams of clay were added and resultant mixture filtered. The filtrate weighed 1842 grams and was then distilled to 150? C. at 5 mms. pressure. In this way 149' grams of unreacted pinene were recovered. The remaining product, 1693 grams, was a clear, viscous oil containing 12.5 per cent sulfur and 5.1 per cent phosphorus. This'product is referred to hereinafter as Product III.

EXAMPLE IV The procedure described in Example III above was carried out with gum spirits of turpentine oil, used in place of pinene. The final product was similar to that obtained with pinene but was slightly cloudy in appearance. It contained 11.8 percent sulfur and 4.8 per cent phosphorus, and is referred to hereinafter as Product IV.

I Thereaction involved in the preparation of the reaction products contemplated herein, and illustrated by the foregoing examples, is novel inasmuch as it is characteristic of only some of the terpenes. As shown above, this reaction is characteristic of the dicyclic terpenes. It is not, however, characteristic of the monocyclic terp'enes, nor is it operative for all aromatic compounds containing one or more unsaturated sidechains. For example, a very different reaction takes place between a phosphorus sulfide and a m'onocyclic terpene when the reaction conditions are those used in the preparation of the contemplated reaction products of dicyclic terpenes. This is illustrated by the reaction between P285 and dipentenega typical monocyclic terpene characterized by twounsaturated bonds, described'be, low in Example V.

EXAMPLE V J ableevolution of hydr gen sulfide occurred throughout the reaction andthe walls of l the fre actionvessel werecoated withan insoluble sludge. Only 76 per cent of the weight of the reactants aluminum phenate of wax'-*phenoi (4 18) r and this product was hydrolyzed with water ountaining ;srna1l amounts of alcohol, such as butanol; whereupon tetrawax-phenol or wax-phenol wssrecovered, the product being ayiscous, cloudy 5 (4-18) was obtained. w l oil which did not give a clear 1 per cent solution Parenthetical expressions (A-B), such as in a petroleum oil. On analysis it was found to (448) above, are used in connection with the contain 6.8per cent sulfur and 2.9 per cent phoswax-substituted hydroxyaromatic compounds, phorus, an indication that an appreciable portion and the esters obtained therefrom, to designate: of the phosphorus and sulfur present in the P285 (A) the number of atomic proportions of chloused was lost in the reaction. This loss was to rine in chlor-aliphatic material reacted with one insoluble sludge and gaseous productstsuch as moi of hydroxyarornatic compound in the Friedei; hydrogen sulfide. V Crafts reaction, and (B) the chlorine content of The procedure shown iri Examplev was also the chlor-aliphatic material. In this example, followed with another typical monocyclic terpenc, A=4 a d 3:113, terpinolene, and the results werer similarto those J l s H W h t exa l t a i onsiderablhw (0 Preparatzon of Zetrawtgm-substrtuted phenyl drognsulfidewas evolvedduring the reaction, an j b f?? e insoluble sludge was formecLand there was a loss ne hundred gra s f W -p no1(418 ,o of phosphorus andsulfurg Q tainedin (b) abovfiiwere reacted with about 15 jjThat the reaction invowed in thepreparatlon grams of benzoyl chloride for about twenty minqrmedie cne terpene-phosphorus sulfide reacutes, with the temperature ranging from about tion p'roducts contemplated herein is specificeto 125 C. to about 150 C; The reaction product was thedicyclic terpenesis further evidencedrbyrthe then washed with water containing small tact that an olefinic hydrocarbon terpenegtypiamounts, as about 2%, of butanol. The product field by myrcene, reacts with a phosphorusfsiilfide so obtainedis Waxphenyl benz oate (448), also inYa manner analogous to that of the monocyclic designated tetrawax-substituted phenyl benzoate terpenes. Furthermorelflerpene jalcoholsgflsuch (31-18). For ease in handling, this productwas aslterpin'eol, and terpene ketones, such as item blended with one half its weight of S.'A. E. 10 chone, reacted with phosphorus sulfides; in the grade mineral oil. n t

same manner as didthe monocyclic terpene's, a Thap ilcompositions comprising only a viscous typifiedby dipentene andterpinolene. I I mineral oil fractionandatypicalprimary oxidw @Illustratie of theestrs contemplated herein tion inhibitor have altendency to developfahaze is tetrawax'e substitutedphenyl benzoate described is illustrated byftest results set forthinTabl 1 belowin Example VI. a below Q These tests also reveal that a' small o 1 amount o fla typical secondary inhibitor efiec l VI l tively corrects this undesirable characteristic 'rewiawix suesmeist2mm BENZOATLE i w n d i i l fraction cbntainmg h l l l l n l primary inhibitor. Thesetests further demon 21W) v i fl 9; 97 93 40. strate that waxphen ols and esters of the type Petroleum bwax of A. S, T. M. melting point of contemplated herein but with shorter chain alkyl 126YF.(5 2 C.),,andhaving1a molecular weight ubst t n lw r n ffe iv in retarding haze; of; about 350,was c hlorinated by introducingchlo (P1 9 1 used i this 11 Pa v m f b "(6' 5 y tn 13% by a Saybolt Universalviscosity of seconds-at 210 weighfof hl r lwas absorbed. a a p 45 F. The test samples were maintained at room in l. y n n fi temperature :(202 5C. andthe number oi days f P Ti m f #W P W? 3 before haae developed in each was noted." The Qne hundred grams of thechlorwaic obtained results of these tests are presented below in in (drive mixed with 12 grams of phenol,;and Table 1.

Tablel Primer? 8 d int" gong; A Inhibitor (cghgcr Secon ary In itor (cinner ppearance nliroduct IIIL. 1.0 .Ql .l Hazeinfidays. Do 1.0 Wax-phenyl benzoate (4-18), 2:1 blendin mineral 0.33 No haze in 29 days.

oil (S. U. V.=45 secs. 210? F r l r l 1.0 W ax-phenyl phthalate (4A2) .v 0.33 D0. 2.0 Hazeinfidays. 2.0 Wax-phcnyl benzoate (418),ab0ve. 0.66 Nohaze in 29 days. 2.0 Wax-phenyl phth'alate (412). 0.66 D0. 3.0 Haze inlday. i 3'0 Waxplienyl benzoate (4 -l 8), above 1.0 No haze in 29days. 3,0 Wax-phenylphthalate (&12) L0 Do. 1.0 Hazeinfidays. 1.0 Wax-phenol (3- 0.33 Haze in7days. 1.0 a 1.0 D0. 3:0 Hazeinlday. 3g0 Diamylphenylbenzoate 0 63 Do. i

III above.

3 "grainsofAlC1a were added at about65 Cwat a rate slow enough to avoid excessive foaming caused by the evolution of hydrogen chloride. The reaction temperature [was then raised to abbut1-75" C5 and thcmixture was stirred for about one hour at this temperature to complete the i'eactibnw The product at this stage was rthe Product III here is from a separate batch but ptcpared essentially the method described in Example The results shownabove in Table 1 demonstrate that haze formation in oil containing a primary oxidation inhibitona pinene-PzS5 reaction product, is appreciably inhibited by adding thereto a small: amount of the secondary inhibitor. The cooperative :action of the twoinhibitors is also demonstrated by similar test results obtained assumes.

7 by. mixing a primary, oxidation inhibitor and a secondary inhibitor and then adding the resulting mixture to the 011- (S. U.- V-.'=45 seconds at 210 F.) i The latter results are shown in Table 2 following.

8 with amounts of the order of 0.1- -1.0% referred. Accordingly, the amount of secondary inhibitor used generally is from about 0.001% to about 5%. c

As indicated hereinabove, the primary and Table 2 lar'imary Cone. v(acne.

. i (Vgghger Secondary Inhibitor g ger Appearance Yroduct IIL. I 1.0 Haze in 7 days.

. no l. 0 Wax henyl benzoate (448), 2:1 blend 111 mineral 0.1 Haze in 16 days.

Do i l. d 0.33 Haze m 37 days. Do i. 1. 0 N0 haze in 77 days.

f As contemplated herein, outstanding oil compositions are obtained by incorporating in an oil a product, obtained b reacting a primary oxidation inhibitor with a secondary inhibitor. A

product of this type is illustrated below in Example VII.

EXAMPLE VII Pinene (426 grams). was heated to 120 C. and P335 (174. gramsF-a molar ratio of 4:1-was added slowly over a period of 55 minutes. This mixture was then heated to 150 C. and maintained at this temperature for 1 hour.

A quantity (117 grams) of the abovepinene- PzSs reaction product was then mixed with 41.5 grams of mineral 011 (S. U. V.=45 seconds'at 210 F.) and with 41.5 "grams of the above described wax phe'nyl benzoate (4-18) (containing /'i of its weight of mineral oil). The resulting mixture wa then heated at 150? C. for one hour at 6-8. mms. "pressure to remove volatile componame. When the reaction product obtained in this'mannerjwas blended in oil (S. U. V.=45 seconds at 210 F.) to provide a 1% blend, there was no haz'e in 'the oil until 63 days had passed. In contrast, the product obtainedby similarly treatinglfl grams of the pinene-Past reaction product with 83 grams of the same mineral oil hazed in" the oil, a 1% blend showing haze in 7 days.

Still another means for counteracting the haze problem is that illustrated by Example VIII below.

EXAMPLE VIII One hundred grams of pinene, 50 grams of an S. A. E. 10 grade mineral oil and 50 grams of wax-phenyl benzoate (4-18) (described in Ta ble 1 above) were warmed to 110 C. and 41 grams of P285 were added thereto. The ratio of pinene to P285 is 4:1. The reaction mixture-so obtained was heated at 150 C. for one hour, and was thereafter heated to 150 C. under vacuum, thereby removing volatile products. The reaction prodnot thus obtained was blended in oil (S. U. V.=45 seconds at'210 F.) to provide a 3% blend; the blend was still clear "after standing 10 days, whereas the same oil containing 3% of Product III, to which this product may be compared, developed a-haze after 1 day.

The amount of secondary inhibitor necessary to effect the desired inhibition will depend upon concentration of primary inhibitor in the oil and will also depend upon the type of. mineral oil fraction used. In general, however, from-about "10% to about 100% byweight of the secondary inhibitor based upon the primary inhibitor present will substantially inhibit haze formation. The amount of primary oxidation inhibitor which-is generally used in oil is from about 0;01% toabout secondary inhibitors of this invention may be incorporated in a viscous mineral oil traction in any one of several ways. For example, a secondary inhibitor may be added to an oil fraction containing a primary inhibitor, or the primary inhibitor added to an oil fraction containing .a secondary inhibitor. Also, the secondary inhibitor may be added to the reactants used in the preparation of the primary inhibitor--namely, a phosphorus sulfide and a dicyclic terpeneand in such case will be present during the reaction. It appears that, under such conditions, the secondary inhibitor reacts with the phosphorus'sulride and the dicycli'c terpe'ne to form a complex product. The product obtained in this manner is then added to the oil fraction. Still another procedure. which may be used involves adding the secondary inhibitor to the reaction mixture of the phosphorus sulfide and dicyclic terpene before the completion of the reaction; then a small amount of the resulting product is added to an oil fraction. Another procedure is that of reacting the dicyclic terpene-phosphorus sulfide reaction product with the secondary inhibitor at an elevated temperature, such as C. to (3., such as shown in Example VII above, and then adding the desired amount of the resulting reaction product to the oil. It willbe apparent, therefore, that the mineral oil compositions of this invention are complex in nature for it is possible that the primary inhibitor and the secondary inhibitor may be present individually in a mineral oil fraction, or may also be present therein as a physical combination or, further, may be present therein in the form of a single chemical composition. In the same connection, it will also be apparent that a primary inhibitor and a secondary inhibitor in a mineral oil composition of the type contemplated herein may enter into chemical reaction when the oil composition is used as a lubricant under certain conditions such, for example, as a lubricant in an engine operating at relatively high temperatures.

In view of the foregoing, the term mineral oil I composition, as used herein and as recited in all of the appended claims is inclusive of all mineral oil factions containing a primary oxidation inhibitor and a secondary inhibitor, and is inclusive of oil compositions obtained or prepared by any of the several procedures hereinabove described. Thus, any of the oil compositions obtained or prepared many of the foregoing procedures is substantially free of haze normally occurring in an oil composition containing a primary oxidation inhibitor but not containing a secondary inhibito'r. V I Mineral oil concentrates are also contemplated herein, "such concentrates containingysubstantially larger concentrations of primary inhibitor and secondary inhibitor than those enumerated if 9 above. That is, relatively largefiamountsof :the said materials may be incorporated in an oil fraction in which they are readily soluble, and the oil concentrateso obtainedlmay thereafter be diluted with a suitable quantity of the said ,5

oiliraction prior ftouser a i i It is to be understood that the examples, procedures and oil compositions: described hereinabove are illustrative only andnot to beconstrued as limitingthe scope of this invention thereto. r10

'For example, all dicyclicterpenes as broadly described above may be used in placeofthose shown in Examples I through IV. ,Correspondingly, any phosphorus sulfide may be used in place of phosphorus "pentasulflde shown in the examples, Q

but the latter is preferred; Also the mineral oils disclosed above are but typical of all viscous mineral oil fractions which may be used, herein. iFlnallygth'e secondary inhibitors shown above are preferred. of this class :but are only representative of the various esters or organic carboxylic acids and wax-substituted hydroxy-aromatic compounds; 1 i i a H This invention is a: continuation-in-part of application Serial No; 482,482, filed April 9,1943, r

i by the present applicants; EverettW. Fuller, and 'Henry S. Angel/with John H. McCracken; oil compositions containing the dicyclic terpenephosphorus sulfide reaction products described 'hereinaboveform the subject matterflof said application Serial No. 482,482: U Weclaim: 1 1 i a 1; Amineral-oilcomposition normally susceptibleto the formation of haze therein; comprising a viscous mineral oil cfractionvcontaining a minor 'proportiong-sufficient to stabilize said oil fraction against the deleteriouseflects of oxidation,uof a phosphorus and sulfur-containing reaction 1 product obtained by reaction, at a temperature phorllssulfideand a'material selected from the group consisting of a dicyclic terpene and an essential oil predominantly comprised of a dicyclic terpene"; andhaving in combination therewith a minor proportion, sufficient to suppresses theformation of haze therein, of a wax-substituted hydroxyaromatic ester of an organic carboxylic acid. 1 i 1 2. A mineraloilcomposition normally *susceptible to the formation of haze therein, com

prising a viscous mineral oil fraction containing a minor proportion, sufficient to stabilize said oil fraction against the deleterious effects of oxidation, of a phosphorusand sulfur-containing reaction productobtained by reacti0n,at a tern- "perature oi from about 100 C, to about 190 jC., of a phosphorus sulfide and a material selected from the group consistingofa dicyclic terpene and anessential oil predominantly comprised of -a"*dicyclic terpene, and having in chemical com-- dation, of a phosphorusand sulfur-containing 7 "reaction product obtained by reaction, at 1 a temperature between about 100 C. and about 160 C., of a phosphorussulfideand a material selected from the group consisting of a dicyclic terpene and an essential oil predominantly com- 7 5 "on normally susprised of a "dicyclic terpene, and having in combination therewith a minorproportion, sufiicient to suppress the formation of haze therein, of a wax-substituted 'hydroxyaromatic ester ofan organic carboxylicacid, 1 i 4. A mineral ,oil composition, normally susceptible to the formation of haze therein,comprising a viscous mineral oilfraction containing a minor proportion sumcient to stabilize said oilfraction against the deleterious eiiects of oxidation, of a phosphorusand sulfur-containing reaction product obtained by reaction, at a temperature of from about C. to about-19030., of substantially one molof phosphorus; sulfide and four wmols of a material: selected from the group consisting of v a dicyclic terpene and an essential oilwpredominantly comprised of a, dicyclicterpenaand having in combination therewith a minor proportion, sufficient to suppress the formation ofhaze therein, of a wax-substituted, hydroxyaromatic ester ofan organicfcar boxylic acid. i;

5. A mineral oil composition normally-wsus; ceptible to theformation of hazevtherein, com;- prising a viscous mineral oil fraction containing a minor proportion, sufficient to stabilizesaicl oil fraction against the deleterious efiectsof oxidation, of a phosphorusand suliur-containingl re action product obtained by reaction, at a temperature between about 100, C. and about 0., ofwsubstantiallyone mol ,of phosphorusmentasulfide and four mols of a material selected-from the group consisting of a dicyclic terpene; andan essentialjoilpredominantly comprised of a dicyclic terpene, and having in combination therewith a ,minor proportion, suflicient to suppress the formation of haze therein, ofa, wax-substituted hydroxyaromatic ester of an organic carboxylic acid. I of from aboutlOO C. toabout 0., of aphosx6. A- mineral oil composition normally-sus- ,ceptible to the formation of haze therein, com,- =prising a viscous mineral oil fraction containing 'of substantially one mol oiphosphorus pentasulfide and four mols of a material selected from the group consisting of adicyclic terpene and an essential oil predominantly, comprised of a-,dicyclic terpene, said material being admixed :with .a diluent substantially inert intsaid reaction, and having? in combination therewith, a minor proportion, sufficient to suppress the formation of haze therein, of a wax-substituted hydroxyaromatic ester of an organic carboxylicjacid.

7. Amineral oil composition normally susceptible to the formation of haze therein, comprising a viscous: min'eralioil fraction containing a minor proportion, sufi'icient to stabilize said all fraction against the deleterious effects of oxidation; ofia phosphorusandsulfur-containing reaction product obtainedby reaction, at a' temperature' be- "tween about 100 C.and' about 160' C.,"of 1'sub stantially one mol of phosphorus pentasulfi'de and iourinolsofpinene, and having in combination therewith a minorproportion, sufficient to suppress the formation of haze therein, of a waxsubs'tituted hydroxyaromatic ester of an organic carboxylic acid.

8. Amineral oilcomposition normally susceptible to the formation of haze therein,comprising a viscous mineral oil fraction containing a minor proportion, sufficient tostabilize saidoil fraction droxyaromatic ester of an aromatic 11 against the deleterious effects of oxidation, of a phosphorusand'sulfur-containing reaction product obtained by reaction; at a temperature between about 100 C. and about 160 C., of substantially one mol of phosphorus pentasuifide and four mols of pinene, said pinene being admixed with substantially an equal weight of a petroleum oil-diluent substantially inert in said reaction, and

having in combination therewith a minor proportion, sufiicient to suppress the formation of haze therein, of a wax-substituted hydroxyaromatic ester of an organic carboxylic acid.

9. A mineral oil composition normally susceptible to the formation of haze therein, comprising a viscous mineral oil fraction containing a minor proportion, sufficient to stabilize said oil fraction against the deleterious effects of oxidation, of a phosphorusand sulfur-containing reaction product obtained by reaction, at a temperature between about 100 C. and about 160 C., of substantially one mol of phosphorus pentasulfide and four mols of turpentine oil, and. having in combination therewith a minor proportion, sufficient to suppress the formation of haze therein, of a wax-substituted hydroxyaromatic ester of an organic carboxylic acid.

10.-A mineral oil composition normally susceptible to the formation of haze therein, com prising a viscous mineral oil fraction containing a minor proportion, sufficient to stabilize said oil fraction against the deleterious efiects of oxidation, of a phosphorusand sulfur-containing reaction product obtained by reaction, at a temperature between about 100 C. and about 160 0., of substantially one mol of phosphorus pentasulfide and four mols of turpentine oil, said turpentine oil being admixed with substantially an equal weight of a petroleum oil diluent substantially inert in said reaction, and having in combination therewith a minor proportion, suflicient to suppress the formation of haze therein, o'fa wax-substituted hydroxyaromatic ester of an organic carboxylic acid.

11. A mineral oil composition normally susceptible to the formation of haze therein, comprising a viscous mineral oil fraction containing a minor proportion, suflicient to stabilize said oil fraction against the deleterious effects of oxidation, of a phosphorusand sulfur-containing reaction product obtained by reaction, at a temperature of from about 100 C. to above 190 0., of substantially one mol of phosphorus pentasulfide and four mols of pinene, and-having in combination therewith a'minor proportion, sufficient to suppress the formation of haze therein, of a wax-substituted hydroxyaromatic ester of an aliphatic carboxylic acid.

12. A mineral oil composition normally susceptible to the formation of haze therein, comprising a viscous mineral oil fraction containing a minor proportion, sufllcient to stabilize said oil fraction against the deleterious effects of oxidation, of a phosphorusand sulfur-containing reaction product obtained by reaction, at a. temperature above about 100 C. of substantially one mol of phosphorus pentasulfide and fourmols of pinene; and having in combination therewith a minor proportion, suiiicient to suppress the for-- mation of haze therein, of a wax-substituted hycarboxylic acid.

13. A mineral oil composition normally susceptible to the formation of haze therein, comprising a viscous mineral oil fraction containing a minor proportion, sufilcient to stabilize-said oil 12 fraction against the deleterious effects of oxidation, of a; phosphorusand sulfur-containing reaction product obtained by reaction, at a temperature between about C. and about C.', of substantially one mol of phosphorus pentasulfide and four mols of pinene, and having in combination therewith a minor proportion, sufllcient to suppress the formation of haze therein, of a wax-phenyl benzoate.

14..A mineral oil composition normally susceptible to the formation of haze therein, comprising a viscous mineral oil fraction containing a minor proportion, sufficient to stabilize said oil fraction against the deleterious effects of oxidation, of a phosphorusand sulfur-containing reaction product obtained by reaction, at a. temperature between about 100 C. andabout 160 0.,

of substantially one mol of phosphorus pentasulfide and substantially four mols of pinene, and

having in combination therewith a minor proportion, sufficient to suppress the formation of haze therein, of tetrawax-phenyl benzoate.

15. A mineral oil composition normally susceptible to the formation of haze therein, comprising a viscous mineral oil fraction containing a minor proportion, suflicient to stabilize said oil fraction against the deletrious efiects of oxidation, of a phosphorusand sulfur-containing reaction product obtained by reaction, at a temperature between about 100 C. and about 160 0., of substantially-one mol of phosphorus pentasulfide and four mols of pinene, and having in combination therewith a minor proportion, sufficient to suppress the formation of haze therein, of a wax-phenyl 'phthalate.

. 16. A mineral oil composition normally susceptible to the formation of haze therein, comprising a viscous mineral oil fraction containing a minor proportion, sumcient to stabilize said oil fraction against the deleterious effects of oxidation, of a phosphorusand sulfur-containingreaction product obtained by reaction, at a temperature between about 100 C. and about 160 C., of substantially one mol of phosphorus pentasulfide and four mols of pinene, and having in combination therewith a minor proportion, sumcient to suppress the formation of haze therein, of tetra-wax phenyl phthalate.

17. A mineral oil composition normally susceptible to the formation of haze therein, comprising a viscous mineral oil fraction containing a minor proportion, from about 0.01 per cent to about 5.0 per cent, of a phosphorusand sulfurcontaining reaction product obtained by reaction, at a temperature of from about 100 C. to about C., of aphosphorus sulfide and a material selected from the group consisting of a dicyclic terpene and an essential oil predominantly comprised of a dicyclic terpene, and having in combination therewith a minor proportion, from about 0.001 per cent to about 5 per cent, of a waxsubstituted ,hydroxyaromatic ester of an organic carboxylic acid. V

18. A mineral oil concentrate comprising a viscous mineral oil fraction having in admixture therewith: 1) a phosphorusand sulfur-containing reaction product obtained by reaction at a temperature of from about 100 C. to about 190 C. of a phosphorus sulfide and a material selected from the group consisting of a dicyclic terpeneand an essential oil predominantly comprised of a dicyclic terpene and (2) a minor proportion of a wax-substituted hydroxyaromatic ester of an organic acid; the quantity of said reattion product and of said ester in said concen- 13 H t trate being greater than about 5.0 per cent, the relative proportlonsof said reaction product and said ester therein being such that when said concentrate is diluted with mineral oil, the mineral oil composition so formed will contain from about 0.01 per cent to about 5.0 per cent of said reaction Number product and from about 0.001 per cent to about 5.0 per cent of saidester.

a EVERETT W. FULLER.

HENRY S. ANGEL.

REFERENCES CITED The following references are of record in the file of this patent:

Certificate of Correction Patent No. 2,455,668. December 7, 1948.

EVERETT W. FULLER ET AL.

It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows:

Column 2, line 45, for thone read than; line 47, for action is read action 1 product is; column 3, line 55, for the word those read these; column 8, line 63, for factions read fractions; column 9, line 62, claim 2, for therein, a read therein, of a; column 11, line 51, claim 11, for above read about; line 65, claim 12, strike out above about 100 C. of and insert instead of from about 100 0. to about 190 0.; column 12, line 27, claim 15, for deletrious read deleterious;

and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 24th day of May, A. D. 1949.

THOMAS F. MURPHY,

Assistant Commissioner of Patents. 

